System and growth method using germanium oxide reactant in chemical vapour deposition growth for production of rutile germanium dioxide template and thin film

Abstract

The subject of the present disclosure provides the production of N-type or P-type or semi-insulating rutile germanium dioxide templates and thin films in order to obtain sun-blind photo detectors from optical systems in the ultraviolet (UV) wavelength, or to obtain UV light emitting diodes, or to produce semiconductor materials required for UV laser diode production, especially for use in the field of power electronics in the defence industry and / or in missile and aircraft tracking systems. The disclosure describes a system and a method for growing r-GeO2 (rutile germanium dioxide) template and thin films using the chemical vapour deposition (CVD) method.

Description

[0001] SYSTEM AND GROWTH METHOD USING GERMANIUM OXIDE REACTANT IN CHEMICAL VAPOUR DEPOSITION GROWTH FOR PRODUCTION OF RUTILE GERMANIUM DIOXIDE TEMPLATE AND THIN FILM

[0002] Technical Field

[0003] The present disclosure relates to the semiconductor materials required for the production of UV laser diodes and the production of solar-blind photo detectors from optical systems in the ultraviolet (UV) wavelength, especially for use in the field of power electronics in the defence industry and / or in missile and aircraft tracking systems. The present disclosure describes the system and method for growing rutile germanium dioxide (r-GeC ) templates and thin films using the chemical vapour deposition (CVD) method.

[0004] State of the Art

[0005] Germanium is a chemical element with the symbol Ge. It is shiny, hard-brittle, grayish- white and has a silicon-like appearance. It is a metalloid in the carbon group that is chemically similar to its neighbouring groups silicon and tin. Rutile germanium dioxide (r-GeO2) has recently been announced as an ultra-wide energy band gap (Eg = 4.48 eV) semiconductor that can be both N-type and P-type doped and can show the relevant conductivities based on theoretical calculations. (Chae et al., 2019) In ongoing studies, the electron and hole effective masses were calculated as 0.23 mo and 1 .23 mo, respectively. (Mengle et al., 2019) These values have made r-GeO2 much more advantageous in terms of electron and hole transfer than semiconductors such as AIN (aluminium nitride) and p-Ga20o (beta gallium oxide), which have an effective hole mass of 3.3 mo and 40 mo, respectively, whose experimental research and development processes are ongoing. The cost of high-crystal quality AIN films is another disadvantage of this material. In order to obtain r-GeO2-based power electronics and UV optoelectronic (photo detector, LED, laser diode) devices, it is necessary to produce high-quality r-GeO2 substrates or templates or thin-film device layers. The chemical vapour deposition method (CVD) is a process used to produce high-purity solid materials. This method, which has been used since the early 1900s, is widely used in the semiconductor industry to produce thin films. In the traditional CVD process, a heated substrate located in the chamber is exposed to one or more gaseous components to deposit or accumulate on it. Chemical reactions occur on or near the hot surface to deposit a thin film of the surface. These processes are accompanied by by-products consisting of unreacted precursor gas discharged from the vacuum vessel. CVD processes generally differ according to activation processes and conditions. They have synthesis conditions where reactors can be hot or coldwalled, pressure can take values greater than vacuum and atmospheric pressure, carrier gas is used or not, and typical temperature range is 200 to 1600<C. In addition to these conditions, there are also improved CVD processes such as plasma, ion, photon, laser, hot filaments or combustion reactions to increase the deposition rate and / or reduce the deposition temperature.

[0006] In the document named “Shallow Valence Band of Rutile GeO2 and P-type Doping” https: / doi.org / 10.1021 / acs.ipcc.0c07757 in the state of the technique, r-GeOz single crystal ingots with very high point defects of 0.5 x 0.3 x 0.2 mm3were obtained at the end of a 15-day growth process using the flux method. Since the relevant growth is both slow, defective and limited to small ingots, the relevant method will be insufficient for technological device production.

[0007] The document numbered JP2023159007A in the state of the art describes the production of unintentionally doped (uid) r-GeO2 crystal substrates and templates by producing GeCk precursors with the hybrid vapour phase epitaxy (HVPE) system. In the relevant study, r-GeO2 production with a macro defect density of less than 5000 cm-2on the structure surface was achieved at growth temperatures of 600<C and above under conditions of 300 pm / h growth speeds on crystal substrates with diameters of 50 mm and above.

[0008] Document numbered US10593544B2 in the prior art describes a method covering lithium gallium oxide, indium oxide, aluminium gallium oxide and indium gallium oxide semiconductors and found to contain no GeO as a precursor.

[0009] Document numbered KR101635970B1 in the state of the art relates to a technology for growing a high-quality germanium single-crystal thin film grown on a silicon substrate containing a silicon oxide layer to which a transfer process can be easily applied. In the system used, processes for growing a germanium thin film on a silicon oxide using a low-pressure chemical vapour deposition (LPCVD) for the production of a germanium single-crystal thin film are mentioned. In terms of the method and raw materials used, germanium oxide was not used as a reactant and neither crystal structure nor thin film formation was provided.

[0010] In the document named "Establishment Of A Growth Route Of Crystallized Rutile GeO2 Thin Film (D1 Mm / H) And Its Structural Properties" (https: / / doi.Org / 10.1063 / 5.0060785) in the state of the art, r-GeOz thin films (001 ) were grown on r-TiO2 substrates by chemical vapour deposition method. In order to optimize the growth conditions, the decomposition processes of Ge source (CeHioGe207) were analysed by thermogravimetry-differential thermal analysis. It was found that GeO2 was synthesized from CeHioGe207 in aqueous vapour at 553-783 ‘C. In terms of the method and raw materials used, germanium oxide was not used as a reactant to form r-GeO2 thin film.

[0011] In the document named "Germanium Thin Film Formation By Low-Pressure Chemical vapour Deposition" (htfe; / ^ix.dgLprg / 10 002fehjn.199732012) in the state of the art, thin films of polycrystalline germanium were formed by pyrolysis of germanium gas in a low-pressure reactor. In the document numbered W02007015897A2 that is also in the state of the art, a chemical vapour deposition (CVD) process for the preparation of multilayer structures containing Ge or Ge-containing layers for use in electrical, optical and photovoltaic applications is described. It generally comprises multilayer structures containing a Ge layer in combination with a Si layer or a SiGe layer. The embodiments comprise multilayer structures with two or more layers containing a Si and Ge alloy. In terms of the method and substrates used, germanium oxide was not used as a reactant, instead different bases and substrates were used and both crystal structure and thin film formation were not provided.

[0012] The document titled "Crystallization Of GeO2 Thin Films Into A-Quartz: From Spherulites To Single Crystals" in the prior art reported successful solid state crystallisation of a thin amorphous GeO2 film into quartz on various substrates including AI2O3, MgA C , MgO, LaAIC ve SrTiO. At relatively low annealing temperatures, the crystallisation process is spherical. As the annealing temperatures gradually increase, quartz crystals begin to form. The process of controlling the growth and synthesising single crystal quartz with crystal sizes of hundreds of microns obtained on sapphire substrates is described. In the document numbered US8815714B2 in the state of the art, a method of forming a germanium thin film on an underlying film, the formation of a germanium seed crystal layer by adsorbing a germanium on the surface of the underlying film using an aminogermane-based gas, and the formation of a germanium-based thin film on the germanium seed crystal layer using a germanium are described. When the aminogermane-based gas is fed to the surface of the silicon oxide film under the above process conditions, hydrogen (H) is separated from the hydroxyl group on the surface of the silicon oxide film and chemically bonds to the nitrogen and hydrocarbon group to form an amine (Cx Hy N) that becomes volatile. The germanium is then combined with the (Ge) bond and the (Cx Hy) group is separated. In this way, the germanium seed crystal layer containing germanium is formed on the surface of the silicon oxide film. The method used, substrates and processing are different.

[0013] When the state of the art is reviewed, a r-GeO2 template and thin film production method and system that do not contain Cl or C as a precursor, can be grown as undoped, n, p and semi-insulating types based on GeO precursor, have a growth plane X-ray diffraction rocking curve (RC) scanning (XRD) maximum half full width (FWHM) of 0.3 degrees and can reach high crystal quality at a growth speed ranging from 0.1 to 5 pm / s and diameter sizes of 50 mm and above are not explained. In the methods described, - there are more than one type and system of the relevant method - different substrates and reactants are used to obtain thin films or germanium crystals or seed crystals using different substrates such as silicon and quartz, which include the application of the chemical vapour deposition method in different ways. The system and method of undoped (unintentionally doped) rutile germanium dioxide template or thin film epitaxial growth method, which basically produces germanium monoxide in gaseous form and obtains it as a result of chemical reaction in the presence of oxygen gas on a single crystal substrate, has not been encountered in the state of the art. For this reason, it has been neccesary to conduct an R&D study in this field.

[0014] The Aim of the Invention The aim of the invention is to provide a system and method that provides the formation of germanium monoxide in gas form on a single crystal substrate by using the epitaxial growth method of pure rutile germanium dioxide template or thin films and then the chemical vapour deposition (CVD) method in the presence of oxygen gas.

[0015] The aim of the invention is to obtain a system and production method in which germanium oxide is used as a reactant in the growth of rutile germanium dioxide template and thin film using the chemical vapour deposition method.

[0016] The aim of the invention is to obtain a growth system that comprises at least one or a combination of several of the system components of a solid dopant heating area, Ge source heating area, substrate heating area, cabin where the reaction takes place, solid dopant crucible, Ge source crucible, single crystal substrate, base holder / rotator platform.

[0017] The aim of the invention is to provide the production of germanium monoxide by conducting oxygen, carrier gas, oxygen-carrier gas mixture on a pure germanium elemental source.

[0018] The aim of the invention is to obtain the production of germanium monoxide by transferring it with carrier gas, oxygen or carrier gas-oxygen mixture after the reaction formed by the mixture of hexagonal germanium dioxide and pure germanium elemental sources in the heating crucible.

[0019] The aim of the invention is to provide the N-type rutile germanium dioxide template or thin film by forming germanium monoxide in gas form based on the epitaxial growth method onto the single crystal substrate by transferring the gas form containing one or more of Sb, As and F atoms to the environment where oxygen and carrier gas are present.

[0020] The aim of the invention is to provide the P-type rutile germanium dioxide template or thin film by forming germanium monoxide in gas form based on the epitaxial growth method onto the single crystal substrate by transferring the gas form containing one or more of Al, Ga, In atoms to the environment where oxygen and carrier gas are present.

[0021] The aim of the invention is to provide semi-insulating rutile germanium dioxide template or thin film by forming germanium monoxide in gas form based on the epitaxial growth method onto the single crystal substrate by transferring the gas form containing one or more of Fe, Mg, Zn, Co, Ni, Cu atoms to the medium where oxygen and carrier gas are present.

[0022] The aim of the invention is to obtain N-type, P-type, semi-insulating rutile germanium dioxide template or thin films by transferring oxygen, carrier gas, carrier gas-oxygen mixture to the source where the solid state elemental, compound or mixture of these is located in the heating pot.

[0023] The aim of the invention is to obtain the gas / gases to be transferred from solid sources for doping purposes at temperatures of 400°C - 1000°C, under pressure below 50 Torr, under conditions where the total gas flow rate is below 500 seem and the ratio of the carrier gas flow rate to the oxygen flow rate in the oxygen-carrier gas mixture is below 100.

[0024] The aim of the invention is to ensure that the growth of N-type, P-type, semi-insulating rutile germanium dioxide template or thin films is obtained on single crystal substrates with diameters of 10 mm and above, with a growth rate of less than 5 pm / h and a total thickness of less than 100 pm.

[0025] The aim of the invention is to form and transport the GeO(g) form used in the growth of N-type, P-type, semi-insulating rutile germanium dioxide at the specified source between 700°C - 900°C, 0.5 Torr - 100 Torr total gas pressure, and 10 - 1000 seem total gas flow rate.

[0026] Description of Drawings

[0027] Figure - 1 Rutile Germanium Dioxide Template and Thin Film Growth System Components View

[0028] Figure - 2 XRD Omega-2 Theta Scan Graphs of Sample Grown on a-Plane Sapphire and Reference Substrate

[0029] Figure - 3 XRD Omega Scan Graph Performed on Rutile Germanium Dioxide Plane

[0030] Figure - 4 AFM Scan View Performed on Rutile Germanium Dioxide Plane

[0031] Reference Numbers 1 . Solid Dopant Heater

[0032] 2. Germanium Source Heater

[0033] 3. Base Heater

[0034] 4. Cabin Body

[0035] 5. Solid Dopant Crucible

[0036] 6. Germanium Source Crucible

[0037] 7. Base

[0038] 7.1 . Single Crystal Substrate

[0039] 8. Base Holder

[0040] 9. Transfer line

[0041] A. Solid Dopant Gas Reactant

[0042] B. Ge Source Gas Reactant

[0043] C. Gas form Dopant Reactant

[0044] D. Oxygen (O2) and Carrier Gas

[0045] G. Germanium Monoxide Gas

[0046] Detailed Description of the Invention

[0047] The invention describes a system and method for growing rutile germanium dioxide (r- GeO2) templates and thin films using the chemical vapour deposition (CVD) method. It is the process of obtaining undoped (unintentionally doped) rutile germanium dioxide (r-GeO2) templates or thin films by forming germanium monoxide in gaseous form based on the epitaxial growth method and by chemical reaction on the single crystal substrate (7.1 ) on the base (7) in the presence of oxygen gas.

[0048] The production of germanium monoxide (GeO) can be achieved in the invention by two different methods. The first of these methods is provided by transferring oxygen or carrier gas or oxygen-carrier gas mixture over the pure germanium (Ge) elemental source. The second of the methods is obtained by transferring the reaction formed by the mixture of hexagonal GeO (germanium oxide) and pure germanium elemental sources in the germanium source heater (2) with the carrier gas or oxygen or carrier gas-oxygen mixture. After this, the production of templates or thin films for r-GeO2 production in N-type, P-type or semi-insulating form is carried out. The formation of N-type r-GeO2 template or thin film is achieved by forming germanium monoxide (GeO) in gas form based on the epitaxial growth method and transferring one or more of the atoms of antimony (Sb), arsenic (As) and fluorine (F) to the medium where oxygen and carrier gas are present on the single crystal substrate (7.1 ). Here, the Sb doping is obtained by transferring oxygen or carrier gas or carrier gas-oxygen mixture to the sources containing elemental or compound Sb in solid form or to the mixture of both in the solid doping heater (1 ). As doping is obtained by transferring oxygen or carrier gas or carrier gas-oxygen mixture to the solid elemental or compound (e.g. AS2O3 - arsenic trioxide) containing As sources or a mixture of both in the heater (1 ) or by transferring As doping directly to the substrate by thermal treatment of compounds containing As in gaseous form (e.g. AsH3- Arsine). F doping is obtained by transferring compounds containing F atoms in gaseous form (e.g. F2- Fluorine) directly to the substrate by thermal treatment.

[0049] P-type r-GeO2 template or thin film epitaxial growth method is basically obtained by forming germanium monoxide (GeO) in gaseous form and transferring one or more of aluminium (Al), gallium (Ga), indium (In) atoms to the medium where oxygen and carrier gas are present on the single crystal substrate (7.1 ). Here, Al doping is obtained by delivering carrier gas to the solid state elemental source in the heater (1 ). Ga doping is obtained by delivering oxygen or carrier gas or carrier gas-oxygen mixture to the solid state elemental, compound (Ga2Oa - Gallium(lll)Oxide) or mixture thereof source in the heater (1 ). In dopant is obtained by delivering oxygen or carrier gas or carrier gas-oxygen mixture to the solid state elemental, compound (ln2O3- Indium(lll)Oxide) or mixture thereof source in the heater (1 ).

[0050] Semi-insulating r-GeO2 template or thin film epitaxial growth method is basically obtained by forming germanium monoxide in gas form and transferring the gas form containing one or more of the atoms of iron (Fe), magnesium (Mg), zinc (Zn), cobalt (Co), nickel (Ni), copper (Cu) to the medium where oxygen and carrier gas are present on the single crystal substrate (7.1 ). The dopands here are also obtained by transferring oxygen or carrier gas or carrier gas-oxygen mixture to the source where the solid state elemental, compound or mixture of these is placed in the heater (1 ).

[0051] GeO(g) (germanium monoxide gas form) used in the above-described growth of N- type r-GeO2 and P-type r-GeO2 and semi-insulating r-GeO2 is formed and transported to the solid state elemental source between 700°C and 900°C at a total gas pressure of 0.5 Torr to 100 Torr and a total gas flow rate of 10 - 1000 seem. In addition, in the growth of the N-type r-GeO2 and P-type r-GeO2 and semi-insulating r-GeO2, the oxygen or oxygen-carrier gas (inert gas) mixture is transferred to the single crystal substrate (7.1 ) via a transfer line (9). It is carried out on single crystal substrate (7.1 ) (especially a-sapphire) with a total gas pressure of 0.5 Torr to 100 Torr, a total gas flow rate of 10 seem to 1000 seem, and a ratio of the carrier gas flow rate in the mixture to the oxygen flow rate of less than 10. In addition, it has been achieved to obtain N-type r-GeO2 and P-type r-GeO2 and semi-insulating r-GeO2 growth on single crystal substrate (7.1 ) with a growth rate of less than 5 pm / h and a total thickness of less than 100 pm with a diameter of 10 mm and above.

[0052] In N-type r-GeO2 and semi-insulating r-GeO2 growth, the gas to be transferred from solid sources for doping purposes is obtained at temperatures between 400°C and 1000°C, at pressures below 50 Torr, with a total gas flow rate below 500 seem and under conditions where the ratio of the carrier gas flow rate to the oxygen flow rate in the oxygen-carrier gas mixture is below 100.

[0053] In N-type r-GeO2 growth, N-type doping with gas source is obtained by transferring gaseous compounds containing As and / or F directly onto the substrate (7.1 ) with or without mixing with the carrier gas at a total flow rate of 100 seem and below.

[0054] The system for growing different types of rutile germanium dioxide (r-GeO2) templates and thin films using the chemical vapour deposition (CVD) method comprises the reaction chamber body (4) that allows the growth process to be carried out safely with solid dopants and Ge source, the base (7) which is the growth chamber where the single crystal substrate (7.1 ) is located, the rotatable base holder (8) that holds the base (7), and the transfer line (9) that provides the transfer of gaseous reactants (A, B, C, D, G) to the base (7). The system comprises a solid dopant crucible (5) to which solid dopant sources are added. The system comprises a solid dopant heater (1 ) which enables the solid dopants in the solid dopant crucible (5) to be converted into gaseous form and the temperature of the crucible (5) to be controlled. The system comprises a germanium source crucible (6) to which germanium (Ge) sources are added. The system comprises a germanium source heater (2) which enables the Ge dopant in the source crucible (6) to be converted into gaseous form and the temperature of the crucible (6) to be controlled. The system comprises a base heater (3) which enables the temperature of the base (7) to be controlled. The system comprises a base holder (8) which enables the substrate (7.1 ) on said base (7) which is the growth chamber to be rotated during growth. The system comprises a source crucible (6) which enables the germanium reactants transferred in gaseous form to be mixed in the shower head geometry.

[0055] The system components are shown in Figure-1. There are three basic regions in the reaction cabin body (4). The growth chamber where the substrate (7.1 ) is located is the base (7) and the substrate heater (3) regulates its temperature. The temperature of the germanium source crucible (6) where the germanium sources are located is controlled by the germanium source heater (2). The temperature of the solid dopant crucible (5) where the solid dopants are located is controlled by the solid dopant heater (1 ). The solid dopant crucible (5) can be multiplied for different dopants. The base holder (8) is the growth chamber and enables the rotation of the base (7) where the substrate (7.1 ) is located during the growth of templates or thin films of r-GeO2 types.

[0056] The single crystal substrate (7.1 ) is located in the growth chamber where the reactants (A, B, C, D) transferred in gas form with the germanium source crucible (6) are mixed in the shower head geometry. There are four reactants and transfer lines (9) carrying the gases (A, B, C, D) seen in Figure-1. The reactants and gases in this transfer line are the dopant gases (A) sent to the dopant chamber and obtained from there, the gases sent to the Ge source chamber and the germanium monoxide gases obtained from there (B), the reactants containing dopants in direct gas form (C), the O2 and carrier gases (D) applied directly onto the substrate (7.1 ).

[0057] The chemical vapour deposition (CVD) method comprises the process steps of: converting germanium monoxide into gaseous form, adding elemental atoms or compounds in solid form to the solid dopant crucible (5) and converting them into gaseous form by heating them in solid dopant heaters (1 ), transporting the solid dopants converted into gaseous form to the transfer line (9) with oxygen and carrier gas, transferring the gas carried into the transfer line (9) towards the single crystal substrate (7.1 ) on the base (7), transporting the germanium monoxide in gaseous form to the transfer line (9), and transferring the germanium monoxide in the transfer line

[0058] (9) to the medium where the dopant oxygen and carrier gas are located on the single crystal substrate (7.1 ). The conversion of germanium monoxide (GeO) into gaseous form involves the process step of obtaining it by transferring oxygen or carrier gas or oxygen-carrier gas mixture over pure germanium elemental source. The conversion of germanium monoxide into gaseous form involves the process step of adding pure germanium elemental source to germanium source crucible (6) and heating it with germanium source heater (2). The conversion of germanium monoxide into gaseous form involves the process step of obtaining it by transferring the gas released after the reaction formed by the mixture of hexagonal GeO and pure germanium elemental sources with carrier gas or oxygen or carrier gas-oxygen mixture. The conversion of germanium monoxide into gaseous form takes place between 700°C and 900°C, at a total gas pressure of 0.5 Torr to 100 Torr and at a total gas flow rate of 10 seem to 1000 seem. The process comprises the process step of adding hexagonal germanium dioxide and pure germanium elemental sources to the germanium source crucible (6) and heating with the germanium source heater (2). In the step of adding the elemental atoms or compounds in solid form to the solid dopant crucible (5) and converting them to gas form by heating in the solid dopant heaters (1 ), at least one of the elemental or compounds in solid form is Sb or As or F or Al or Ga or In or Fe or Mg or Zn or Co or Ni or Cu atoms. In the step of adding the elemental atoms or compounds in solid form to the solid dopant crucible (5) and converting them to gas form by heating in the solid dopant heaters (1 ), the process comprises the process step of obtaining N-type rutile germanium dioxide by transferring the gas forms of Sb or As or F elements or compounds to the substrate together with GeO and oxygen carrier gas. The process comprises the process step of obtaining the solid form elemental or compound Sb containing sources heated by solid dopant heater (1 ) or by conveying oxygen, carrier gas or carrier gas-oxygen mixture to the mixture of both. The process comprises the process step of obtaining the solid form elemental or compound As containing sources heated by solid dopant heater (1 ) or by conveying oxygen, carrier gas or carrier gas-oxygen mixture to the mixture of both or by conveying the compounds containing As in gaseous form directly to the substrate (7.1 ) by heat treatment. The process comprises the process step of obtaining the compounds containing F atom in gaseous form by heating them in solid dopant heater (1 ) and by conveying the gaseous form directly to the substrate (7.1 ). In the step of adding elemental atoms or compounds in solid form to the solid dopant crucible (5) and converting them into gaseous form by heating in solid dopant heaters (1 ), the process comprises the process step of obtaining P-type rutile germanium dioxide by transferring the gaseous forms of Al or Ga or In elements or compounds onto the substrate (7.1 ) together with GeO and oxygen carrier gas. The process comprises the process step of obtaining the Al elemental source in solid dopant heater (1 ) by transferring it onto the substrate (7.1 ) together with carrier gas. The process comprises the process step of obtaining the Ga dopant in solid dopant heater (1 ) by transferring the elemental or compound form or mixture of these into the source together with oxygen, carrier gas or carrier gas-oxygen mixture. The process comprises the process step of obtaining the In dopant in solid form in solid dopant heater (1 ) by transferring the elemental or compound form or mixture of these into the oxygen, carrier gas or carrier gas-oxygen mixture. The process comprises the process step of obtaining semi-insulating rutile germanium dioxide by transferring the gaseous forms of Fe or Mg or Zn or Co or Ni or Cu elements or compounds to the substrate together with GeO and oxygen carrier gas in the step of adding elemental atoms or compounds in solid form to the solid dopant crucible (5) and converting them to gaseous form by heating in solid dopant heaters (1 ). The process comprises the process step of obtaining the elemental or compound forms of Fe, Mg, Zn, Co, Ni, Cu dopants in solid dopant heater (1 ) by transferring oxygen, carrier gas or carrier gas- oxygen mixture to their mixture. The total gas pressure on the substrate (7.1 ) on the base (7) is between 0.5 Torr and 100 Torr, and the total gas flow rate is between 10 seem and 1000 seem. In the transfer line (9) the gas carried towards the single crystal substrate (7.1 ) on the base (7) in the step of transferring the single crystal substrate (7.1 ) is a- plane sapphire or r-TiO2 or 3C-SiC or 4H-SiC or 6H-SiC.

[0059] The most basic aspect of the invention is the formation of the GeO(g) compound and the realising the growth. The relevant compound is obtained on the Ge source single crystal substrate (7.1 ) with two different methods. The gaseous form of germanium monoxide obtained by the reaction of solid germanium and oxygen or by the reaction of solid h-GeO2 with solid germanium is shown below. (Reactions I and II)

[0060] I. h-GeO2 (k) + Ge(k) — > GeO(g)

[0061] II. Ge(k) + O2 (g) — > GeO(g)

[0062] In order for the reaction number one to be efficient, the sources in powder or small granule form with dimensions not exceeding 1 cm were mixed and used with a molar ratio of approximately 1 :1. The GeO(g) formed at a suitable temperature via the germanium source heater (2) is transferred onto the single crystal substrate (7.1 ) via the transfer line (9) with the help of carrier gas.

[0063] For the reaction number two, the surface area of the Ge(S) source that comes into contact with oxygen is important. This type of source usage has a reducing effect on GeO(g) transfer by reacting with GeO(g) and 02(g) in the system. (The relevant reaction is given below as the reaction number three)

[0064] III. GeO (g) + O2 (g) — > h-GeO2 (k)

[0065] For this reason, in order to minimise the above reaction number three, O2 should be given to the relevant source together with the carrier gas mixture. Carrier gases are preferably selected as Ar or N2. Different gases can also be selected in different embodiments of the invention.

[0066] Another important reaction for Ge sources is given below as the reaction number four;

[0067] IV. Ge (k) + O2 (g) — > h-GeO2 (k)

[0068] The above reaction has a source transfer inhibitory effect. The conditions in which the relevant reaction is dominant over the reaction number one in which gaseous germanium monoxide is obtained are the conditions in which the 02(g) partial pressure is relatively high. For this reason, the given reactions must be suppressed.

[0069] Sapphire or r-TiO2 or 3C-SiC or 4H-SiC or 6H-SiC and similar substrates (7.1 ) can be preferred as single crystal substrate (7.1 ). In particular, a-plane sapphire was used in the invention. As a result of the magnification, r-GeO2 film was obtained on a-plane sapphire. X-ray diffraction (XRD) omega-2 theta scans of the obtained film and a- sapphire reference substrate are given in Figure-2. As can be seen, a single crystal structure r-GeO2 film with a very high XRD peak intensity could be obtained. The magnification speed was obtained as approximately 1 .5 pm / s with the measurements made. The growth rate may vary in different preferred applications of the invention.

[0070] The XRD omega scan of the r-GeO2 peak is shown in Figure - 3. The full width at half maximum (FWHM) value measured as 478 arcsec indicates good crystal quality. In the AFM scan shown in Figure - 4, it was measured that the growth was in step-flow geometry and the average surface roughness was 4.57 nm.

[0071] Sample shaping and growth results related to the invention are included in the figures. However, the invention is not limited to the examples given. It is possible to obtain successful results suitable for the content given above with different modifications. Therefore, it should be taken into consideration that the present invention does not only consist of different embodiments of the invention used and exemplified in the invention description.

Claims

CLAIMS1. A system for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method, characterized by comprising:- a reaction cabin body (4) that ensures the growth process with solid additives and germanium source is carried out safely,- a base (7), which is the growth chamber where the single crystal substrate (7.1 ) is placed,- a movable base holder (8) that holds mentioned base (7), and- a transfer line (9) which enables the gaseous reactants (A,B,C,D,G) to be transferred to mentioned base (7).

2. The system for growing different types of rutile germanium dioxide templates and thin films using vapor deposition (CVD) method according to Claim 1 , characterized by comprising: a solid dopant crucible (5) to which solid dopant sources are added.

3. The system for growing different types of rutile germanium dioxide templates and thin films using vapor deposition (CVD) method according to any of the previous claims, characterized by comprising : a solid dopant heater (1 ) which enables the solid dopants in mentioned solid dopant crucible (5) to turn into gas form and to control the temperature of the crucible (5).

4. The system for growing different types of rutile germanium dioxide templates and thin films using vapor deposition (CVD) method according to any of the previous claims, characterized by comprising: a germanium source crucible (6) to which germanium dopant sources are added.

5. The system for growing different types of rutile germanium dioxide templates and thin films using vapor deposition (CVD) method according to any of the previous claims, characterized by comprising: a germanium source heater (2) which enables the germanium dopant in the dopant crucible (6) to turn into gaseous form and the temperature of the crucible (6) to be controlled.

6. The system for growing different types of rutile germanium dioxide templates and thin films using vapor deposition (CVD) method according to any of the previous claims, characterized by comprising: a base heater (3) which allows the temperature of mentioned base (7) to be controlled.

7. The system for growing different types of rutile germanium dioxide templates and thin films using vapor deposition (CVD) method according to any of the previous claims, characterized by comprising: a substrate holder (8) which allows the single crystal substrate (7.1) on mentioned base (7) which is the growth chamber to be rotated during enlargement.

8. The system for growing different types of rutile germanium dioxide templates and thin films using vapor deposition (CVD) method according to any of the previous claims, characterized by comprising: the germanium source crucible (6) which allows the germanium reactants transferred in gas form to be mixed in the shower head geometry.

9. A method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method, charazterized by comprising the process steps of: a. converting germanium monoxide into gaseous form, b. adding elemental atoms or compounds in solid form to the solid dopant crucible (5) and converting them to gaseous form by heating in solid dopant heaters (1 ), c. transferring the solid dopants converted into gaseous form to the transfer line (9) with oxygen and carrier gas, d. transferring the gas carried in the transfer line (9) towards the single crystal substrate (7.1) on the base (7), e. transferring gaseous germanium monoxide to the transfer line (9), and f. transferring germanium monoxide in the transfer line (9) to the single crystal substrate (7.1 ) towards the medium where the dopant oxygen and carrier gas are present.10.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 9, characterized by comprising: in the process step “a”, the process step of obtaining oxygen or carrier gas or oxygen-carrier gas mixture by conducting it over a pure germanium elemental source.

11. The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 9 or Claim 10, characterized by comprising : in the process step “a”, the process step of adding pure germanium elemental source to the germanium source crucible (6) and heating it with the germanium source heater (2).12.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 9, characterized by comprising: in the process step “a”, the process step of obtaining the gas released after the reaction with the mixture of hexagonal GeO and pure germanium elemental sources by carrying it with carrier gas or oxygen or carrier gas-oxygen mixture.13.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 12, characterized in that; in the process step “a”, the process is carried out between 700°C and 900°C, at a total gas pressure of 0.5 Torr to 100 Torr and a total gas flow rate of 10 seem to 1000 seem.14.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 9 or Claim 12, characterized by comprising : the process step of adding hexagonal germanium dioxide and pure germanium elemental sources to the germanium source crucible (6) and heating with the germanium source heater (2).15.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according toClaim 9, characterized in that; in the process step “b”, elemental or compound in solid form is at least one of the atoms Sb or As or F or Al or Ga or In or Fe or Mg or Zn or Co or Ni or Cu.16.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 9 or Claim 15, characterized by comprising:, in process step “b”, the process step of obtaining N-type rutile germanium dioxide by transferring the gaseous forms of Sb or As or F elements or compounds onto the substrate together with GeO and oxygen carrier gas.17.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 16, characterized by comprising: the process step of obtaining the solid form elemental or compound Sb containing sources heated by solid dopant heater (1 ) or by conveying oxygen, carrier gas or carrier gas-oxygen mixture to the mixture of both.18.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 16, characterized by comprising: the process step of obtaining the solid form elemental or compound As containing sources heated by solid dopant heater (1 ) or by conveying oxygen, carrier gas or carrier gas-oxygen mixture to the mixture of both or by conveying the compounds containing As in gaseous form directly to the substrate (7.1 ) by heat treatment.19.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 16, characterized by comprising: the process step of obtaining the compounds containing F atoms in the gaseous state by heating them in the solid dopant heater (1 ) and directly transferring the gaseous form onto the substrate (7-1 ).20.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according toClaim 9 or Claim 15, characterized by comprising: in process step “b”, the process step of obtaining P-type rutile germanium dioxide by transferring the gaseous forms of Al or Ga or In elements or compounds onto the substrate (7.1 ) together with GeO and oxygen carrier gas.

21. The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 20, characterized by comprising: the process step of obtaining the solid state Al elemental source in the solid dopant heater (1 ) by transferring it to the substrate (7.1 ) together with the carrier gas.22.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 20, characterized by comprising: the process step of obtaining the Ga dopant in the solid dopant heater (1 ) by transferring the source containing the elemental or compound form of the solid state or the mixture of these onto the substrate (7.1 ) together with oxygen, carrier gas or carrier gas-oxygen mixture.23.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 20, characterized by comprising: the process step of obtaining the In dopant in the solid state in the solid dopant heater (1 ) by introducing oxygen, carrier gas or carrier gas-oxygen mixture into the elemental or compound form or their mixture.24.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 9 or Claim 15 characterized by comprising:, in process step “b”, the process step of obtaining semi-insulating rutile germanium dioxide by transferring the gaseous forms of Fe or Mg or Zn or Co or Ni or Cu elements or compounds onto the substrate (7.1 ) together with GeO and oxygen carrier gas.25.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 24, characterized by comprising: the process step of obtaining theelemental or compound forms of Fe, Mg, Zn, Co, Ni, Cu dopants in solid state or their mixture by conveying oxygen, carrier gas or carrier gas - oxygen mixture to the solid dopant heater (1 ). 26.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 9, characterized in that: the total gas pressure on the substrate (7.1 ) on the base (7) is between 0.5 Torr and 100 Torr, and the total gas flow rate is between 10 seem and 1000 seem.27.The method for growing different types of rutile germanium dioxide templates and thin films using chemical vapour deposition (CVD) method according to Claim 9, characterized in that: in the process step “d”, the single crystal substrate (7.1 ) is a-plane sapphire or r-TiO2 or 3C-SiC or 4H-SiC or 6H-SiC.

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